JPS59211035A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To make the sensitivity extra low by adding a specified compound to an emulsion prepd. in the presence of a rhodium salt or the like. CONSTITUTION:A compound represented by general formula I (where G is halogen, alkyl, alkoxy or hydroxy; R1 is a univalent org. group having <=-0.05 Hammett's sigmap value such as alkyl, hydroxy or alkoxy; R2 is aryl having sulfo; R3 is a univalent org. group; each of X and Y is H or alkyl; X and Y may bond to each other to form a 5- or 6-membered ring; and (m) is 1-4) is incorporated into a layer of an emulsion prepd. in the presence of a water soluble rhodium salt and/or a water soluble iridum salt. The amount of the salts is 1X 10<-6>-1X10<-2>mol per 1mol silver halide. The resulting photosensitive material has improved safety to light and is easily handled in a daylight room. It has high contrast and improved shelf stability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more particularly to an ultra-low sensitivity light-sensitive material for light room use.

[Prior art]

In recent years, in the printing field, due to the complexity of printed matter and the development of scanners, there has been a demand for improved efficiency in the turning process. In response to this demand, improvements have been made in terms of equipment such as printers 2-- and in terms of photosensitive materials. 1 of the return film
Photosensitive materials with a sensitivity of 0-4 to 10-5 have been developed.

As a method of reducing the sensitivity of photosensitive materials, water-soluble rhodium salts such as cupric chloride and pdium chloride are added to silver halide emulsions.
Methods of using water-soluble iridium salts such as iridium chloride and organic desensitizers such as pinacryptol yellow and phenosafranine are generally known. Among these compounds, methods for making photosensitive materials ultra-low sensitivity include: It is preferable to add a water-soluble rhodium salt or a water-soluble iridium salt to the silver halide emulsion, but this light-sensitive material must be handled in a bright room that blocks ultraviolet light to shorten the safelight time. However, it has drawbacks such as soft gradation and increased sensitivity and gradation changes during storage before processing, so it cannot fully satisfy market demands as a photosensitive material for bright room use. Since this was not possible, further improvements were desired.

[Object of the Invention] The present invention provides a silver halide photographic light-sensitive material that improves the various drawbacks of light-sensitive materials for use in bright rooms as described above.

The purpose of the present invention is to improve the relationship between safelight properties and sensitivity in the use of photosensitive materials that can be handled in a bright room that blocks ultraviolet light and is baked with a light source rich in ultraviolet light, and to provide even higher contrast while being stored. It is an object of the present invention to provide a photosensitive material with extremely little increase in sensitivity and change in gradation.

Other objects of the invention will be understood from the description herein.

[Structure of the invention]

The photosensitive material according to the present invention includes 1. /%l: I An emulsion layer consisting of a silver halide emulsion prepared in the presence of a water-soluble rhodium salt or/and a water-soluble iridium salt in an amount of lXl0' to lXl0-2 mol per 1 mol of silver genide, or an emulsion layer other than the above-mentioned emulsion layer. It is characterized by containing a small amount of a compound represented by the following general formula in the constituent layers of the light-sensitive material.

General formula symbol (R3) m-1 ■ t2 In the formula, G is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group (for example, methoxy group, ethoxy group, etc.) % R1 represents one organic group with a Hammett's σp value of less than -0.05,
2 represents an aryl group having one sulfo group, 3 represents one organic group, X and Y represent a hydrogen atom and an alkyl group, respectively, and X and Y are bonded to each other to form a 5-membered ring. Alternatively, a 6-membered ring may be formed.m is 1 to 4
represents an integer.

In a preferred embodiment of the invention, R1 is Hammett's σ,
Represents one organic group having a value smaller than -0.05, preferably an alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, n-butyl group, tertiary-butyl group) , carboxymethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, benzyl group, phenethyl group, etc.), cycloalkyl group (e.g. cyclopentyl group, cyclohexyl group, etc.), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group) , n-butoxy group, 2-methoxyethoxy group, ethoxymethoxy group, 2-hydroxyethoxy group, etc.), amine group (e.g. amino group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, anilino group, etc.) ),
Ureido group (e.g. ureido group, methylureido group,
ethylureido group, etc.).・~Met's σ, value is [Structure-activity relationship of drugs] (Nankodo) p. 96 (197
9), and substituents can be selected based on this table.

R2 is a 7-aryl group having one sulfo group, and the aryl group can further contain other substituents such as halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group, n-proxy group, etc.), aryloxy group (e.g. phenoxy group, etc.), number of carbon atoms 1 to 4
Alkyl groups (e.g. methyl, ethyl, 1-propyl, n-butyl, etc.), carboxy groups, alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, etc.), nitro groups, alkylsulfonyl groups (e.g. methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group), carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group) etc.), a sulfonamide group (for example, a methylsulfonamide group, an ethylsulfonamide group, etc.), and the like.

Specific examples of R2 are, for example, 3-sulfophenyl group, 4-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-chloro-4-sulfophenyl group, 4-chloroμm3-sulfophenyl group, 2-μp-5-sulfophenyl group, 2-methoxy-4-sulfophenyl group, 2-
Hydroxy-4-sulfophenyl group, 2.5-dichloro-4-sulfophenyl group, 2.6-dimethyl-4-sulfophenyl group, 4-phenoxy-3-sulfophenyl group, 2-chloroμm6-methyl-4- Sulfophenyl group, 3
-Carboxy-2-hydroxy-5-sulfophenyl group, 2.5-disulfophenyl group, 3.5-disulfophenyl group, 3.6-disulfo-α-naphthyl group, 8-hydroxy-3,6- Examples include a disulfo-α-naphthyl group, a 5-human ρ-xy7-sulfo β-naphthyl group, and a 6,8-disulfo-β-naphthyl group.

R3 represents one organic group, preferably having 1 to 1 carbon atoms.
4 alkyl groups (e.g. methyl, ethyl, n-
butyl group), halogen atom (e.g. fluorine atom,
(chlorine atom, bromine atom, etc.), hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), nitro group, etc.

X and Y each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tertiary-butyl group, etc.) Substituents such as cyano group,
Halogen atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxy groups, alkoxy groups (e.g. methoxy groups).

ethoxy group, n-p-poxy group), carboxy group,
Alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), 7-syl group (e.g. acyl group, prupionyl group, etc.), 7-syloxy group (e.g. acyloxy group, prupionyloxy group, etc.),
7-aryloxy group (for example, phenoxy group, etc.), 7-mino group (for example, t%f amino group, methylamino group, dimethylamino group, diethylamino group, anilino group, etc.), alkylthio group (for example, methylthio group, ethylthio group, etc.), Alkylsulfonyl groups (e.g. methylsulfonyl group, ethylsulfonyl group, etc.), acylamino groups (e.g. acetylamino group, etc.), alkylsulfonylamino groups (e.g. methylsulfonylamino group, ethylsulfonylamino group, etc.), aryl groups (e.g. phenyl group) etc.) may be replaced by 1. Furthermore, X and Y may be combined with each other to form a 5-membered ring or a 6-membered ring (
Specifically, a ring such as a bipridyl group, a piperidino group, or a morpholino group may be formed. m represents 1.2.3 or 4.

The compound represented by the general formula used in the light-sensitive material of the present invention is, for example, [The Cyanine Dice and Fists Rated Compounder J].
Dyes and Re1ated Compound
s).

Published in 1964) "The Chemistry of Synthetic Dice"
f8ynthetic Dyes) Published in 1971)
It can be easily produced by the synthetic method described in ``Dye Handbook'' (Marukubi, published in 1970).

Next, specific examples of the compounds represented by the above general formula used in the present invention will be shown.
It is not limited to these.

[Exemplary compounds]

S O3N a SO3N a 03Na S 03 Na 11- 8 O3N a 12- 803 N a S O3N a 14- S O3N a 803K S O3N a 03K 03K S O3N a 18- S O3N a 803 N a S 03 N a 03Na S 03 Na 803 Na (b) 03Na 22- The compounds represented by these general formulas may be used alone or in combination of two or more. However, if chemical ripening is performed, it is effective to add it after chemical ripening, and if chemical ripening is not performed, it is effective to add it after physical ripening and before coating on the support. .

In addition, these compounds may be added to the rogensed steel emulsion layer or the constituent layers of the photosensitive material adjacent to this emulsion layer, such as the protective layer,
It can also be added to intermediate layers and the like.

The amount added is 0.01 to 1 mole of silver halide.
A suitable value is 10t, but a range of 0.1 to 5v is preferred.

As the silver halide used in the emulsion of the light-sensitive material of the present invention, silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, or a mixture thereof is used, but in any case, silver chloride is The content is preferably 60 mol% or more, preferably 80 mol% or more.

Examples of water-soluble rhodium salts used in the present invention include rhodium dichloride, rhodium trichloride, and ammonium hexachlororhodate. Preferably, complex compounds such as rhodium trichloride and halogen are preferred; Water-soluble iridium salts include iridium trichloride,
Examples include iridium tetrachloride, potassium hexachloroiridate [phase]ate, and sodium hexachloroiridate hydroxide. These may be used alone or in combination for 2 seconds or more.

The amount of these additions is 1 x 10-
6 to I X 10-2 mol, but I X 10-5
~1×10 mol is more preferred. If the amount of the water-soluble rhodium salt or water-soluble iridium salt exceeds 10@-2 moles of I.sub.X, the object of the present invention cannot be achieved because, although there is still a tendency for desensitization, the tone becomes softer. On the other hand, if it is less than 1.times.10@-6 mol, the sensitivity will not drop to the level required for a photosensitive material for bright room use, which is the objective of the present invention, and the objective will not be achieved.

In the present invention, the water-soluble rhodium compound and iridium compound are present during the preparation of the halogenated complex emulsion, and this preparation refers to the process of emulsion and physical ripening.
It may be added by any method at any time during this process. However, the preferred addition time is the time of emulsification, and a particularly preferred addition time is when a water-soluble rhodium salt is added to the halide solution.
This method is prepared by adding a water-soluble iridium salt. This is because in order to maximize the high contrast desensitization effect of rhodium or iridium, rhodium atoms or iridium atoms must be uniformly distributed inside and on the surface of silver halide grains, and for this purpose they are added to the halide liquid. There is a need. On the other hand, when 25- is added during physical ripening, rhodium atoms or iridium atoms are thought to be distributed only on the particle surface, making it difficult to achieve the objective of low sensitivity.

Furthermore, as a method for preparing the emulsion, forward mixing, back mixing, semipermeable mixing, and simultaneous mixing are all possible, but simultaneous mixing is the most preferred method.

The reason is the same as above. Further, methods for preparing emulsions include an ammonia method, a neutral method, and an acid method, but these methods tend to increase sensitivity and are not suitable for the purpose of the present invention. The distribution of silver halide grains in the emulsion may be either monodisperse or Petep dispersion, but monodisperse is preferable for uniformity of grain sensitivity. Further, the grain crystal habit may be cubic, octahedral, or any other type. Particle size is 1μ
The thickness is preferably 0.5μ or less. More preferably, the thickness is 0.3μ or less. This is because it is necessary to make the developed silver particles finer in order to prevent them from becoming rough and to achieve the required photographic density with a small amount of silver in order to save resources.

The emulsion thus prepared can also be chemically sensitized (for example, sulfur sensitization, reduction sensitization, etc.) using a chemical sensitizer. However, the object of the present invention can be achieved even without chemical sensitization.

In addition, the emulsions thus prepared may contain stabilizers such as tetrazaindenes, anti-capri agents such as triazoles and tetrazoles, covering power improvers,
It is possible to add irradiation inhibitors such as oxanol dyes and tartrazine dyes, lubricants such as latexes, and other additives used in general photographic emulsions such as spreading agents and hardeners.

The silver halide emulsion used in the present invention is coated on a support, and commonly used supports such as polyester base, baryta paper, laminated paper, glass, etc. are used for binding the support.

As a light source for exposing the photosensitive material thus prepared, a light source rich in ultraviolet light used mainly in the printing field, such as a xenon, metal halide, mercury lamp, or ultra-high pressure mercury lamp, is used.

As the developer for the photosensitive material of the present invention, commonly used developers can be used. As developing agents, dihydroquinone benzenes such as hydroquinone, polyhydroquinone, and catechol, 1-7enyl-3-pyrazolidone, 1-7enyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4- 3 such as methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
-Pyrazolidones, N-methyl-p-7 minophenol, N-(4-hydroxyphenyl)chrysin-yonahalaminophenols, β-methanesulfonamidoethyl, ethylaminotoluidine, N,N-diethyl-p-
Examples include p-phenylene diamines such as phenylene diamine and ascorbic acid. An aqueous solution containing one or more of these developing agents is used, as well as potassium sulfite, formaldehyde sodium hydrogen sulfite, hydroxylamine, and ethylene urea. Preservatives, development inhibitors such as potassium bromide, potassium iodide, 1-phenyl-5-mercaptotetrazole, 5-nitropenzimidazole, 5-nitropentutriazole, 5-nido-indazole, 5-methyl- Penztriazole, 4
- Organic capri inhibitors such as thiazoline-2-thione, alkaline and buffering agents such as sodium carbonate, potassium hydroxide, borax, jetanolamine, triethanolamine, sodium sulfate, sodium acetate, and sodium citrate. salts such as EDTA-2Na, etho-triacetic acid, water softeners such as hydroxyethylenediaminetriacetic acid, developer hardeners such as glutaraldehyde, developing agents such as diethylene glycol, dimethylformamide, ethyl alcohol, benzyl alcohol. A solvent for an organic inhibitor, a development accelerator such as methylimidacillin, methylimidazole, polyethylene glycol having an average molecular weight of 1540, and dodecylpyridinie promide can be added. Although the pH of the developer is not subject to any restrictions, a pH of 8 to 13 is usually used, preferably 9 to 12.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example-1 Simultaneous mixing of a silver chlorobromide emulsion at 40° C. for 50 minutes with a silver bromide content of 4 mol % and the added amount of pdium chloride or/and potassium hexafluoriridate [phase] shown in Table 1. Prepared by method. The emulsion thus prepared was desalted and redispersed to obtain a monodisperse emulsion with an average grain size of 0.21 μm.

pdium chloride or/and hexachloriridium [
Potassium phase] acid was dissolved in sodium chloride solution and added to the halide solution.

Add a small amount of sodium thiosulfate to these emulsions,
Chemical sensitization was carried out at 55° C. for 30 minutes, and 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added as a stabilizer. Next, the compounds and amounts shown in Table 1 were added to these emulsions, and 1-phenyl-5-mercabutotetrazole was added as an anti-capri agent, and HO(0H20H20)1(
OHz +10HO)m (0H20)120), HH
3 (m=20, t+n=15), adding saponin as a spreading agent and mucochloric acid as a hardening agent,
Trowel l is 3. It was coated on a film base so that it became sr/, i and dried.

The sample NaA-J thus obtained was subjected to a safelight test of irradiation for 60 minutes under a thigh color lamp (FL40SW-NU manufactured by Toshiba) at about 300 lux, treated with the following developer, and fog was measured. Immediately after application and temperature 50
The samples were subjected to forced deterioration by leaving them in an atmosphere of 70% RH and 70% RH for 2 days, and then exposed to light through a light wedge using a bright room printer (HMW-215 manufactured by Oak Seisaku Shin) and processed with the following developer.

Developer formulation> The developing conditions were 27° C. and 1 minute and 40 seconds.

The results are shown in Table 2.

Margin Table 1 Comparative Compound No. 1 Table 2 Sensitivity is expressed relative to the sensitivity of Sample F immediately after application as 100.

As is clear from Table 2, samples B and E of the present invention.

F, I, and J have ultra-low sensitivities that can be handled as photosensitive materials for bright rooms, and have an improved safelight property versus sensitivity relationship.
Furthermore, it can be seen that the contrast is high and that there are very few changes in sensitivity and gradation during storage.

Example-2 10 mol% silver bromide and 5x per mol silver halide
A silver chlorobromide emulsion containing 10 moles of rhodium chloride was
It was prepared by a simultaneous mixing method at 0°C for 25 minutes. Rhodium chloride was dissolved in a sodium chloride solution and added to the halide solution. The emulsion thus prepared was desalted and redispersed to obtain a monodisperse emulsion with an average grain size of 0.20 μm. Sodium thiosulfate was added to this emulsion, chemically sensitized at 58°C for 50 minutes, and 6-methyl-4-hydroxy-
1,3,3a,7-tetrazaindene was added, then this emulsion was divided, the compounds of the present invention shown in Table 3 and the comparative compounds shown below were added, and 1 was added as an anti-capri agent.
-Add phenyl-5-mercaptotetrazole, 4,5-dimethyl-4-thiazoline-2-thione as a sensitizer, tartrazine as an irradiation inhibitor, saponin as a spreading agent, and moufchloric acid as a hardening agent. Then, it was coated on a film base and dried so that the silver amount was 3.5y/♂. Sample No. obtained in this way
, 1 to 12 were tested in the same manner as in Example 1, exposed and treated with the following developer. Development conditions were 38℃, 20℃
seconds.

<Pre-development (undiluted) prescription> Before use, 1 t of the above stock solution is diluted with 3 t of water.

Comparative Compound NCL2 803 Na Comparative Compound Nα3 So 3 Na Comparative Compound Na4 SO3N a Below margin 38- Table 3 As is clear from the results in Table 3, the samples of the present invention have significantly improved safelight properties. Furthermore, it can be seen that the contrast is high, and the sensitivity and gradation are stably maintained during storage.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Agent: Patent attorney: Nobuaki Sakaguchi (and one other person) 217

Claims (2)

[Claims] (1) lXl0' to 1x10- per mole of silver halide
An emulsion layer consisting of a silver halide emulsion prepared in the presence of 2 moles of a water-soluble μdium salt or/and a water-soluble iridium salt, or at least one layer of a constituent layer of a light-sensitive material other than the emulsion layer, is marked with the following general formula. A silver halide photographic material containing the compound shown below. 2 In the formula, G represents a halogen atom, an alkyl group, an alkoxy group, or a hydroxy group, and s "l is Hammett's σ, and the value is -0.
2 represents an aryl group having one sulfo group, R3 represents one organic group, X and Y each represent a hydrogen atom,
It represents an alkyl group, and X and Y may be combined with each other to form a 5-membered ring or a 6-membered ring. m represents an integer from 1 to 4. (2) In the general formula mark, one organic group represented by R1 and having a σ value smaller than -0.05 is an alkyl group, a hydroxy group, an alkoxy group, a ureido group, and an amino group. A silver fluoride photographic material according to claim 1, characterized in that: